Apparatus for producing chlorids of carbon.



J. MAOKAYE.

APPARATUS FOR PRODUCING OHLORIDS OF CARBON.

APPLICATION FILED MAR. 20, 1906.

1,009,428. Patented N0v.21, 1911.

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J. MAG AYR' APPARATUS FOR PRODUCING GHLORIDS OF CARBON.

APPLICATION FILED MAR. 20, 1906.

2 I Patented Nov. 21, 1911.

4 SKEET$$HEET 2.

J. MAOKAYE.

APPARATUS FORPRODUOING OHLORIDS OF CARBON.

APPLICATION FILED MAR.20,1906.

Patented Nov. 21, 1911.

4 SHEETSSHEET 3.

oKAYE.

APPARATUS FOR UOING UHLORIDS OF CARBON.

- APPLIG N FILED MAR. 20. 1906. 1,009,428. Patented N0v.21, 1911.

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' leading to the mixing-chambers.

UNITED STATES PATENT, OFFICE.

JAMES MAGKAYE, OF CAMBRIDGE, MASSACHUSETTS, ASSIGNOB TO STONE ANDWEBSTER, OF BOSTON, MASSACHUSETTS, A FIRM.

APPARATUS FOR PRODUCING CHLORIDS OF CARBON.

Specification of Letters Patent.

Patented Nov. 21, 1911.

Application filed March 20, 1906. Serial No. 307,070.

To all whom it may concern:

Be it known that I, JAMES MAOKAYE, of Cambridge, in the county ofMiddlesex and State of Massachusetts, have invented certain new anduseful Improvements in Apparatus for Producing Chlorids of Carbon, ofwhich the following is a specification.

This invention relates to a new and improved apparatus for producingchlorids of carbon.

Figure 1 is a diagrammatic plan view of an apparatus constructed inaccordance with my invention. Fig. 2 is a side elevation of the reactionchamber and its stacks. Fig. 3 is a top plan view of the reactionchamber and stacks shown in Fig. 2. Fig. 4 is a vertical sectional viewof the reaction chamber and the connectionof the chamber with itsstacks. Fig. 5 is a cross-sectional view of the reaction chamber taken.on the line 55 of Fig. 1, looking in the direction of the arrow. 1 Fig.6 is a cross-sectional view of the inlet portion of one of the stackstaken on the line 66=of Fig.2. Fig. 7 is a cross-sectional view of oneof the stacks taken on the line 7-7 of Fig. 2, showing the;

showing the arrangement of the divided.

portion of one of the stacks with its cooling chamber or water-jacket.Fig. 9 is a detail sectional view of the three-way valve for controllingthe passage of the gases to pipes Fig. 10 is a detail view showing themethod of connecting the chlorin inlets of the stacks.

In using my apparatus. I bring methane CH into the presence of chlorinC1 in a closed chamber filled with porous media,

preferably granulated coke that has been GIL-{ACL CCh-l- H-ICl-l-heatwhere 0H,:methane, or'the main ingredient of natural gas; C1,:chlo'rin,a gas;

C(ll ztetrachlorid of carbon, a gas above 76 0., solvent, non-explosive,and non-inflammable; HCl=hydrochloric acid, a gas,

soluble in water.

The methane and chlorin, if permitted to if react without control, willnot produce chlorids of carbon. This uncontrolled reaction may beexpressed as follows: I

out, 1 represents a gasometer for holding.

methane or natural gas, a large percentage of which. is made up ofmethane, as is well known. 2 represents a gasometer for holds ingchlorin, 3 represents a meter, 4; a regulator, 5 a drier, 6 a 3-wayvalve, 7 a pipe leading from the'gasolneter 1 tothe meter 3, 8 a

pipe leading from the meter 3 to the regulator 4, 9 a pipe leading fromthe regulator 4 to thedrler 5, 10 a. pipe leading from the drier 5 tothe 3-way cock 6. The meter 3,

regulator 4, and drier 5 may be of any suitable preferred design orconstruction. The purpose of the drier and the meter are well lmown andrequire no description. The

purpose of the regulator is to maintain a predetermined rate of flow ofthe contents of the gasometer 1 through the system. 12 represents aregulator, 13 a drier, 14 a pipe leading from the chlorin gasometer 2 tothe regulator 12,15 a. 'pipe leading from the regulator 12 to the drier13'. 16 a pipe leading from the drier 13 to a 3-way cock 17. Theregulator 12 is to maintin a predetermined rate of flow from thecontents of the chlorin gasometer through the system. The drier 13 islike drier 5. 20 represents a suitable base or support for holding thechamber 21. 22, 23 represent stacks each connected to one side of thereaction chamber 21 the said stacks and chamber constituting, in eflectone chamber. From the the stack 23 and a pipe 31 leads to the end of thestack 22, while from the 3-way cock 17 a pipe 32 leads to theend of thestack 23 and the pipe 33 leads to the end of the and'any reaction inthemixing zone. Each of the stacks 22, 23, connects at its lower end, asshown in the drawings, with the bottom of chamber 21. From the top ofchamber 21 a pipe 50 leads and connects with a condenser 51. 52represents a pipe connectlng the condenser 51 with the condenser 53. Apipe 54 connects condenser 53 with condenser 55, while a pipe 56connects the condenser 55 with the pump 57, the pump acting as anexhaust to maintain the flow of gases through the system. The condensers55 may be of any suit-able design or construction to hold and condensethe products of the reaction. The reaction chamber should be maintainedin any preferred way at a temperature between 250 and 600 C.

The regulators 4 and 12, as shown, are connected together by shafts 12",4 and gears 4 12 so that the said regulators travel together inpredetermined order with relation to each other. Assuming the regulatorssand 12 to have the same capaclty under the same speed and pressure; asthe amount of chlorin in the mixture is greater than the amount ofmethane, the wheel 12 is made smaller than the wheel 4", it beingunderstood that gearing of any desired speed ratio may be employed. Whenusing this arrangement above described, the ordinary wet gas-meter maybe used for the regulators 4 and 12.

From the foregoing it will be seen that the system starts with twobranches, gasometer 1 for the methane, gasometer 2 for the chlorin, themethane and chlorin branches uniting in the outer end of the stacks 22and 23, the chlorin and methane being brought into the presenceof eachother at this point. From the end of the stacks 22 or 23 the apparatusproceeds as one system up to and including the exhaust pump 57, fromwhich the uncondensed gases may be carried to any desired point. It willbe seen that the exhaust pump 57 is eflective throughout the wholesystem, not only up to the chamber 21 but also through the methane andchlorin branch. At the exhaust end of the system the pressure is lessthan at the feed end, so to speak, which difference in pressure can bevaried as. desired by varying the speed or work of the exhaust 57. Aninspectlon of the drawings shows that I have one control of each branch,chlorin and methane, to wit, the regulators, a control for theregulation of the heat in the reaction chamber, and a control for therate of work, to wit, the exhaust.

My process is carried out as follows ,The gasometers 1 and 2 beingsupplied respectively with natural gas and chlorin, the

cocks 6 and 17 are operated to connect their respective ports with theend of the stack 22 or the end of the stack 23, the purpose being toconduct both the natural gas and the chlorin in combining proportionsinto the end of the same stack. .If carbon tetrachlorid is to be made,the proportion should be, roughly, four parts of chlorin to one part ofmethane; proper allowance being made for any impurities in the gases. Ifchloroform is to be made, the proportions should be, substantially,three parts of chlorin to one part of methane with a similar allowancefor impurities. The dichlor methane, 011 01 or monochlor methane, CH Cl,are produced by this process, ordinarily, only as by-products when thecarbon tetrachlorid or chloroform are being made. If, for any reason, itis desired to make them by this apparatus, the theoretical combiningproportions should be used,-that is, two parts of chlorin to one ofmethane for the dichlor methane and one part of chlorin to one or moreof methane for the monochlor methane. The exhaust 57 is then started.This compels the flow of the natural gas and chlorin in predeterminedquantities through their respective'regulators 4: and 12, into the upperend of the stack 22 or stack 23 or both stacks, according to whether oneor both are being used where the methane and chlorin enter the materialwith which the stacks of the chamber are filled, forming a mixture andthereafter passing as a mixture to that point in the stack or thechamber where the temperature is suflicient to permit the desiredreaction to be accomplished. 'It is Within the contemplation of myinvention to employ any such valve means for regulating the flow of thegases to the stacks as will enable the gases to pass into either stackexclusively, or into both simultaneously, as may be desired. In practicethe temperature for the reaction is about 400 (1, but may vary from 250to 600 C., depending upon the speed of the apparatus, the relativepurity of the ingredients, etc. Any desired means may be employed toestablish in the reaction chamber the desired temperature. As themixture enters the chamber 21,

which by the means hereinafter described has been heated to the requiredtemperature from 450 to 550 0., reaction begins and is completed, theproducts of reaction passing out through the pipe 50. After the reactionhas started in the chamber 21, the zone of reaction works backward intothe inclined parts 22 and .23 of the stacks 22, 23, and. into the lowerpart of the stacks 22 and 23 that are surrounded by water circulation77, such backward travel of the zone of reaction being due to the heatgiven off by the reaction. While the reaction is started in the firstinstance in the chamber 21, yet, after the reaction has commenced, thelower parts of the stacks 22 and 23, their inclined portions 22 and 23,together with the chamber 21, constitute the reaction chamber, since,

- after the reaction is once started, the reaction zone works back-intothe water-jacketed portions of. the reaction-chamber, the temperaturebeing prevented from falling too low by the independent source of heatin the chamber 21, while the temperature is prevented from rising toohigh by means of the water circulation, hereinafter described.'Although, after the process is once well started, the principal reactiongoes on in the water-cooled portions of the reaction chamber, it isadvisable in practice to maintain a temperature in the chamber 21,suflicient to cause reaction which is between 450 and 550 (1., sincethis will prevent portions of the mixture which might come through themain reaction zone uncombined, from going through the apparatus in thatcondition; and will also permit the prompt starting of the process, if,for any reason, it should have to be temporarily discontinued. Thisbackward movement of the zone of reaction enables me in some cases torely upon the reaction itself for the necessary heat after the reactionis once set up. In order to prevent the zone of reaction from extendingtoo far into the stack and encroaching upon the mixi-ng zone, I employany preferred means for so controlling the temperature as to prevent thereaction zone from extending back into the mixing zone, which rearwardaction if not controlled would manifestly interfere with the mixing andthe efiiciency of the apparatus and the method.

The tetrachlorid of carbon and hydrochloric acid together with the otherproducts of reaction among which may be one or all of the following;

CHO13,GH,C1,, 011,01, 0 01,, and 0 01.

pass, as stated, through the pipe 50 into the condenser 51, where thegases are reduced to such a temperature below 76 C., that thetetrachlorid of carbon will liquefy, so that it can be drawn off fromthe condenser and the hydrochloric acid will be dissolved by the waterin the condenser. For commercial purposes the temperature of the gasesshould be reduced to the vicinity of 35 C., in order to dissolve thehydrochloric acid to a sutficient state of concentration so that it canbe drawn OH in commercial form.

The gases that remain uncondensed in the condenser 51 will in likemanner be taken care of by condensers 53 and 55, as many condensersbeing used as is necessary, the residual gases, if any, other than thetetrachlorid of carbon or hydrochloric acid being taken care of by theexhaust.

Reference to Figs. 2 to 8,wwherein I have illustrated my improved formof reaction chamber 21 with its stacks 22, 23, 60 represents a pan,- orother suitable receptacle,

adapted to hold water and maintained on any suitable frame or support,not shown. 61, 62 represent two slats arranged crosswise .of the -pan 60and having a sufiicient length to permit their ends to extend beyond thesides of the pan, as shown, in

order to rest upon and be supported by a nected at its end by bolts 64with the underside of the slat 61 (see Figs. 3 and 4). 65 represents acomplemental slat in like man ner connected to the underside of slat 62by bolts 66. 67, 68 represent I two slats, one near each end of the panhaving their ends extending beyond the edge of the pan and adapted torest upon the support which carries the slats 61, 62, or' any othersupport independent of the support of the pan. 69 represents a slatconnected at its ends by bolts 70, to the underside of the slat 67 (seeFig. 2). 71 represents a slat connected at its ends by bolts 72 to theunderside of the slats 68. The slats 61, 62 serve to support thereaction chamber and at the same time the slats 63, 65, the lattertogether with the slats 69 and 71' serving to support inclinedlongitudinal slats 73. Three of the slats 7 3 are arranged at one end ofthe water jacket, three at the other, each set of three slats forming ineffect a grid, one set of the slats or grid supporting the inclined part22 of the stack-22, while the other set of slats on the right hand .endof the pan supportthe inclined part 23*. of the stack 23.

' By the described construction it will be seen that the watercirculation can be maintained about the inclined parts '22, .23 of thestacks and the lower part of the reaction chamber.21 by means of a pipe210 for introducing a supply of water to the bottom of the water jacketof the stack, and 2.

pipe 211 for removing heated water from the top of the said water.jacket of the stack. Any other preferred means for maintaining thewater circulation may be employed. Gravity, or other form of power, maybe relied upon for maintaining the circulation. In like manner a pipe212 may be employed for introducing. water into the bottom of the pan60, and a pipe 213 may be employed for withdrawing the heated water fromthe pan 60, the circulation being maintained either by gravity, or anyother form of power desired. The lower part of the stack 23 immediatelyabove the inclined part 23 is divided, as shown in Figs. 2, 7, and 8,for a short distance to subdivide the cross-sectional area of the stackand increase the cooling surface by means of the chamber 76. 77represents a water-jacket of any suitable material, arranged about thesubdivided part of the stack 23. This chamber has a closed bottomthrough which the stack passes, but may be open at the top, and watercirculation may be maintained in this chamber about the two branches120, 121, of the stack and through the chamber 76 between said branchesby any desired means. The stack 22 may if desired be formed with a likesubdivision provided with a like water-jacket, itbeing understood thatthe circulation in the water-jacket 77 is or may be lndependent of thecirculation in the pan 60. While I have shown in the drawings a stackdivided into two branches, such subdivisions maybe made into any desirednumber of branches,

the idea being to subd1v1de the stack into a sufficient number ofbranches to enable the cooling media to maintain the desired temperatureby disslpating the heat of the reaction. The upper end of the stack 23is closed and provided with three inlet ports 80, 81, 82, the middleport being for methane or natural gas and the ports 80, 81 for chlorin.The ports 80, 81 being connected by a T, or other connection, 400, towhich the pipe 32 is connected. Two diaphragms 83, 84:, are arranged oneon either side of the port 82 and extend down a substantial distanceinto the stack, permltting the natural gas to enter the stack, butkeeping it separate from the chlorin which enters through the ports 81,80 on either side respectively of the diaphragms 84, 83. -The stack 22in like manner is provided with ports 86, .87, for the chlorin and theport 88 for the natural gas. The ports 86, 87 are connected by a T, orother connecs tion, like 400 (see Fig. 10) to the pipe 33.

This connection for the ports 86, 87, 15 not shown, but is like theconnection shown in Fig. 10 for the ports 80, and 81. The stack 22 isfurther providedwith diaphragms 89 and 90, corresponding to thediaphragms 83, 84. Each of the stacks and their branches 22*, 23 arefilled with comminuted material 100 of any suitable kind to permit themixing of the chlorin and natural gas without explosion. I have found inpractice comminuted coke very satisfactory for this purpose, care,however, being exercised not to have the coke comminuted so fine as tocreate powder to cause back pressure. The coke comminuted material 100in each stack extends substantially up to the point indicated by line66-, that is, above the lower ends of the diaphragms '83 to 84 and 90 to89 so that the chlorin and natural gas are in contact with coke or othermaterial before they come in contact with each other.

The reaction chamber 21 is composed of a piece of soapstone 91, throughwhich is cut a rectangular hole (see Figs. 4 and 5) and is filled withpowdered coke 100; While any desired material may be used for the bodyof the chamber, I have found soapstone very eflicient to withstand thevarious phenomena attendant upon the reaction that takes place, as wellas the action of the mixture and the products of the reaction. The sidesof the soapstone block 91 are preferably covered with lead 92, which, atthe bottom is bent under the lower end of the block, as shown in Fig.then extended downward a short distance and then bent at an angle andextended to form inclined connections 22*- and 23*, with the stacks 22and 23, respectively, thus making the chamber 21, the connections 22,23, and the stacks 22, 23, continuous. The stacks 22, 23, and theirconnections 22, 23 are duplicates. Either or both stacks may be used, orthrown into or out of action.

97 (Fig. 4) represents a block of lead arranged in a pocket formed bythe lead covering 92 and serves as a terminal. This block, as shown, isrectangular in shape and extends the whole length of the chamber, whichat this point is of lead. 102, 103 represent a row of carbon rods, oneon either side of the chamber in the soapstone. The lower ends of theserods are arranged in complemental recesses in the lead terminal 97. Theupper ends of the row of rods 103 are arranged in the carbon terminal104 at the top of the chamber, while the upper ends of the rods 102 arearranged in the carbon terminal 105. 106 represents a car? bon striparranged between the two termi nals 105, 104, and provided with amarginal lip, as shown, engaging the tops of the termmals in order toprevent its slipping downward. 110- represents a dome formed of leadarranged 'over the carbon strip 106} as shown, and over the chamber inthe soapstone. The ends of the sheet of lead forming this dome arecarried down and in-.'

serted in a suitable recess in the soapstone, as shown in Fig. 4.- Thisconstruction leaves a strip, as 301, at the top end of the block 91,uncovered by the lead lining. In order to seal the chamber against aleak of gases at this point, I interpose between the lining at thispoint, and the block 91, a layer of material, such as 302, composed ofcement, or any preferred material capable of reslsting the passage ofgases, but nothaving any substantial conductivity for an electriccurrent. In practice, one'wire 117, from the source of electricalheating, is connected to the lining 110 on one of the inclined parts, asstacks 23, the other wire 116 being connected to the portion of the leadlining forming the extension 110. By this means the current is compelledto pass through the carbon rods, it being understood that the leadlining isof sufiiciently large area to prevent any harmful action duetothe use of the lining as a part of the electric current carryingcircuit. Of course, any other suitable form of connecting the wires upto the heating unit may be employed.

The upper edge of the sheet of lead 92 that covers the soapstone is notturned down, in order to prevent any contact between this and the leadforming the dome. 112, 113 represent two bars one on either side and atthe lower part of the dome. These bars are adapted to be clampedtogether by means of bolts 115 at each end, in order to bind the partsfirmly in position, the carbon strip 106 serving as ,an abutmentagainstwhich the terminals 104 can be pressed. 116 represents a wirerunning from the top of the dome 110 to any suitable source of power.117 represents a wire running from one of the inclined members of thestacks, here shown as 23*, to the source of power, the current passmgfrom the source of power to the stack, thence to the lead terminal 97,

through the rods 102, 103,- to the terminals 104, 105, to the dome 110,thence back. Any

apparatus are designed and intended for I the production of all chloridsof carbon,

includin chloroform, in the same manner. Obvious y, however, theproportions of chlorin and methan'e'should, as above stated,

he changed so as to supply the gases in the proportions proper for theparticular chlorid of carbon desired; but the operator must, regardless.of the product desired,

. proceed asabove described, that is, he must heat the reaction chamberuntil he perceives by-the product obtained, and by the working back ofthe heat toward the mixing zone, that the reaction has begun, and thenhe must be ready to reduce or shut off the interior heat, decrease hisgas supply, or cause it to run through the other mixing arm of thereaction chamber, supply more or cooler water for cooling, or stop thereaction temporarily altogether, if he perceives by the presence of sootin the product, or by the progress of the heat too far backward towardthe mixing zone, that the reaction is becoming too violent; and,conversely, he must be ready to change his gas supply, cut off his coldwater, or increase his interior, heat, if the reaction stops or becomesinefiicient and gases begin to go through unchanged. The proper use ofthese'various steps will readily be understood and applied by onefamiliar with the art, as soon as the idea above set forth of keepingthe reaction zone from working back to the mixing-zone, as aboveexplained, is understood.

Having thus explained the nature of my invention and described a way ofconstructing and using the same, though without attempting to set forthall of the forms in which it may be made or all of the modes of its use,what I claim and desireto secure by Letters Patent is V D 1. Anapparatus for producing chlorids of carbon, comprising a mixing-chamber,filled with a porous medium, means for supplying methane and chlorin tosaid chamber in predetermined proportions, a reaction chamber filledwith a porous medium connected with the mixing chamber, means forheating said chamber to the temperature required to produce the desiredreaction, means for cooling the chamber at a different point to preventthe reaction from working backward into the mixing chamber, and meansfor separating the products of the reaction.

2. An apparatus for producing chlorids of carbon, comprising a reactionchamber filled with a porous medium, a source of heat arranged in saidchamber, means for supplying a mixture of methane and chlorin them to bemixed in one portion or zone thereof, a reaction portion or zone within.

the chamber, and means for bringing said mixture in the zone of reactionto the temperature required for reaction, .means for controlling thezone of reaction with relation to the zone of mixing, and means forseparating the products of reaction.

4. An apparatus for producing chlorids of carbon comprising a chamberfilled with a porous medium, a device within the chamber for supplying avariable amount of heat at one part of the chamber, means for supplyingnatural gas and chlorin to said chamber in predetermined proportions;devices for cooling the chamber between said heatable portion and theentrance point of the gases and means for collecting the products of thereaction.

5. An apparatus for producing chlorids of carbon comprising a. reactionchamber, a porous corrosion resisting filling arranged in said chamber,said chamber being formed with branches, porous filling arranged in saidbranches, a heating device for said chamber, cooling devices for eachbranch ofsaid chamber, means for supplying methane and chlorin inpredetermined proportions to each said branch and cutting ofi suchsupply from any branch, and means for collecting and saving the productsof the reaction.

6 A reaction chamber having a corrosion resisting porous filling andsoapstone walls, and an outlet, and supplied with an internal heatingdevice, sald chamber having branches with lead walls supplied with anexterior cooling device and gas inlets, and means for cutting off thesupply of as from one or all of the branches, as desired.

7. An apparatus for producing chlorids of carbon comprising a mixingchamber, means for preventing reaction during the mixing of the gases, areaction chamber connected therewith, means for subjecting the mixturein the reaction chamber to a reacting temperature, means, including awater circulation for maintaining the re-. acting material at a propertemperature for the proper reaction, and means for separating theproducts of reaction.

8. A reaction chamber having walls composed of non-conducting material,a sheathing connected to said walls, composed of material adapted toresist corrosive action of the contents of the chamber and maintain saidchamber gas tight, said sheathing being extended beyond said walls toform a stack or inlet member, and means for subjecting said stack towater circulation.

. 9. A reaction chamber having Walls composed of non-conductingmaterial, a sheathing arranged upon said Walls, composed of materialadapted to resist corrosive action of the contents of said chamber, andmaintain said chamber gas tight, said sheathing being extended beyondsaid walls to form a stack or inlet member, and means for cooling thewalls of said stack or inlet member.

10. A reaction chamber having walls composed of non-conducting material,a sheathing arranged upon the said walls, composed of material adaptedto resist corrosive action of the contents of the said chamber andmaintain said chamber gas tight, said sheathing being extended beyondsaid walls to form a stack or inlet member, said stack between its endsbeing subdivided to form Y a plurality of passages, the Walls of onepassage being separated from the Walls of the other to permitcirculation of a cooling medium between said walls.

11. An apparatus for producing chlorids of carbon, comprising a reactionchamber with branches, the walls being of material which Will resistcold chlorin, said chamber and its branches being filled with a porouscorrosion resisting material, a lining adapted to resist hot chlorin inthe main body of the chamber within the walls, and heating means withinsaid lined part of the chamber, a liquid cooling circulation about thebranches of the chamber, inlets for chlorin and methane at one end ofthe branches of the chamber, and means for supplying the gases in theproper proportions to said branches and mixing them therein in thepresence of the porous medium before they, are permitted to react, andan outlet for the products of the reaction, and means for collecting andretaining the same.

In testimony whereof I have aflixed my signature, in presence of twowitnesses.

- JAMES MACKAYE.

Witnesses:

